Aromatic polyether nitrile resin composition

Abstract

The present invention addresses the problem of providing an aromatic polyether nitrile resin composition in which the melt viscosity is high, the melt viscosity is reduced without impairing the thermal resistance of an aromatic polyether nitrile having a slow crystallization rate, the crystallization rate is improved, volatile components such as gases are not generated during molding, and moldability is improved. Provided as a solution is an aromatic polyether nitrile resin composition in which: the weight ratio of an aromatic ether nitrile composition (A) to an aromatic polyether nitrile (B) is in the range of (A) / (B) = 1 / 99 to 50 / 50; and the weight average molecular weight (Mw) in terms of polystyrene is at least 45,000 as measured by a gel permeation chromatography analysis. <Aromatic ether nitrile composition (A)> This aromatic ether nitrile composition contains the dihydroxy compound represented by general formula (1) and has a composition satisfying compositions (i) and (ii) in a liquid chromatography (LC) analysis in which ultraviolet rays having a wavelength of 280 nm serve as detectors.　Composition (i): Relative to all components detected by the LC analysis, the area percentage of the dihydroxy compound represented by general formula (1) is in the range of 10% to 95%.　Composition (ii): Relative to all components detected by the LC analysis, the total of the values of the area percentages of the compound represented by general formula (2), the dihalobenzonitrile compound represented by general formula (3), and the dihydroxy compound represented by general formula (4) is no more than 5%. <Aromatic polyether nitrile (B)> This aromatic polyether nitrile has a weight average molecular weight (Mw) in terms of polystyrene of at least 50,000 as measured by a gel permeation chromatography analysis and has the repeating unit represented by general formula (5).

Description

Aromatic polyether nitrile resin composition

[0001] The present invention relates to an aromatic polyethernitrile resin composition that can significantly improve moldability, such as fluidity and crystallization rate, of a heat-resistant resin, without impairing the excellent heat resistance of aromatic polyethernitriles.

[0002] Aromatic ether (co)polymers are useful resins that not only have excellent heat resistance, flame retardancy, chemical resistance, and mechanical strength, but also are thermoplastic and can be molded by heating. Therefore, they can be used to obtain various molded products such as filaments, films, sheets, tubes, pipes, and round bars by molding methods such as injection molding, extrusion molding, and hot compression molding. Aromatic polyethernitriles, which are one type of aromatic ether (co)polymer, have the highest level of heat resistance among thermoplastic resins and excellent mechanical strength (see, for example, Patent Documents 1 to 4). However, due to their excellent heat resistance, aromatic polyethernitriles have a high melting point, high melt viscosity, slow crystallization rate, and poor moldability, which poses a major problem in that the molding cycle cannot be sufficiently shortened when producing molded products by hot molding such as injection molding. To solve this problem, a compound obtained by reacting 4-phenylphenol with dihalogenobenzonitrile has been proposed as a plasticizer that reduces the melt viscosity of aromatic polyethernitriles and improves moldability (see, Patent Document 5). Although it is certainly possible to reduce the melt viscosity of the resin, the problem is that the aromatic polyether nitrile volatilizes as a gas during molding, which requires molding temperatures of 380°C or higher, and this easily leads to molding defects. Attempts have been made to improve the crystallization rate of aromatic polyether nitrile by adding various crystal nucleating agents such as alumina, titanium dioxide, talc, and carbon black, but these have no effect in reducing the melt viscosity (see, for example, Patent Documents 6 and 7). Furthermore, aromatic polyether nitriles containing small amounts of copolymerized components have been disclosed as a method for maintaining crystallinity and lowering the melting point. However, in all cases, the temperature-lowering crystallization temperature is lower than that of polymers composed of the single component, and the crystallization rate is actually reduced (see, for example, Patent Document 8).

[0003] JP-A-59-206433 JP-A-60-147439 JP-A-61-055120 JP-A-62-223226 Special JP 03-134055, JP 62-240353, JP 01-193354, International Publication No. 2021 / 241492

[0004] An object of the present invention is to provide an aromatic polyether nitrile resin composition having improved moldability, in which the melt viscosity is reduced and the crystallization rate is increased without impairing the heat resistance of aromatic polyether nitriles which have a high melt viscosity and a slow crystallization rate, and in which no volatile components such as gases are generated during molding.

[0005] As a result of intensive research to solve the above problems, the present inventors have found that a combination of an aromatic ether nitrile composition (A) having a specific composition and an aromatic polyether nitrile (B) having a specific molecular weight can provide an aromatic polyether nitrile resin composition which does not generate gas during molding, has a reduced melt viscosity without impairing heat resistance, and has an improved crystallization rate, and have completed the present invention.

[0006] The present invention is as follows: 1. An aromatic polyethernitrile resin composition, in which the weight ratio of an aromatic ethernitrile composition (A) to an aromatic polyethernitrile (B) is in the range of (A) / (B) = 1 / 99 to 50 / 50, and the weight average molecular weight (Mw) measured in terms of polystyrene by gel permeation chromatography analysis is 45,000 or more. <Aromatic Ethernitrile Composition (A)> An aromatic ethernitrile composition containing a dihydroxy compound represented by general formula (1), which satisfies compositions (i) and (ii) in liquid chromatography (LC) analysis using ultraviolet light at a wavelength of 280 nm as a detector. Composition (i): The area percentage of the dihydroxy compound represented by general formula (1) is in the range of 10% to 95% of all components detected by the LC analysis. Composition (ii): The sum of the area percentages of the compound represented by general formula (2), the dihalobenzonitrile compound represented by general formula (3), and the dihydroxy compound represented by general formula (4) is 5% or less of all components detected by the LC analysis. (In general formulas (1), (2), and (4), R each independently represents a divalent group represented by general formula (1a) or (1b), and in general formulas (2) and (3), X each independently represents a halogen atom.) (In general formula (1a), R １ each independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, a phenyl group, a phenoxy group, or a phenylalkyl group having 7 to 10 carbon atoms; m represents 0 or an integer of 1 to 4; n represents 0 or 1; p and q represent 0, 1, or 2; and * represents each bonding position. (In general formula (1b), R １ and m are defined as in general formula (1a), Y represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group, Z represents an oxygen atom, a sulfur atom, or non-crosslinking, each Ar independently represents an aryl group having 6 to 8 carbon atoms, and * represents each bonding position.) <Aromatic Polyether Nitrile (B)> An aromatic polyether nitrile having a weight average molecular weight (Mw) of 50,000 or more in terms of polystyrene, as measured by gel permeation chromatography analysis, and having a repeating unit represented by general formula (5). (R in general formula (5) has the same definition as in general formulae (1), (2) and (4).) 2. The aromatic polyethernitrile resin composition according to 1., wherein R in general formulae (1), (2) and (4) of the aromatic ether nitrile composition (A) and in general formula (5) of the aromatic polyether nitrile (B) are not independent and each R is a phenylene group, a naphthylene group or a biphenylene group. 3. The aromatic polyether nitrile resin composition according to 1., wherein the aromatic ether nitrile composition (A) further contains a polymer having a repeating unit represented by general formula (5). (R in general formula (5) is common to general formulas (1), (2) and (4), and each R independently represents a divalent group represented by general formula (1a) or general formula (1b).) 4. The aromatic polyethernitrile resin composition according to 1., wherein the aromatic ethernitrile composition (A) has a weight average molecular weight (Mw) of 500 or more and 8,000 or less, calculated in terms of polystyrene, as measured by gel permeation chromatography (GPC). 5. The aromatic polyethernitrile resin composition according to 1., wherein the weight ratio of the aromatic ethernitrile composition (A) to the aromatic polyethernitrile (B) is (A) / (B) in the range of 10 / 90 to 40 / 60.

[0007] The aromatic polyether nitrile resin composition of the present invention has a low melt viscosity without impairing the heat resistance of the aromatic polyether nitrile resin having high heat resistance, and does not generate volatile components such as gases during molding, thereby improving moldability and making it possible to provide molded articles having excellent heat resistance, mechanical strength, and crystallinity.

[0008] (Aromatic Polyethernitrile Resin Composition of the Present Invention) The aromatic polyethernitrile resin composition of the present invention is characterized in that the weight ratio of the aromatic ethernitrile composition (A) to the aromatic polyethernitrile (B) is in the range of (A) / (B) = 1 / 99 to 50 / 50, and the weight average molecular weight (Mw) measured in terms of polystyrene by gel permeation chromatography analysis is 45,000 or more. <Aromatic Ethernitrile Composition (A)> The aromatic ethernitrile composition (A) contains a dihydroxy compound represented by general formula (1) and satisfies compositions (i) and (ii) in liquid chromatography (LC) analysis using ultraviolet light at a wavelength of 280 nm as a detector. Composition (i): The area percentage of the dihydroxy compound represented by general formula (1) is in the range of 10% to 95% of all components detected by the LC analysis. Composition (ii): The sum of the area percentages of the compound represented by general formula (2), the dihalobenzonitrile compound represented by general formula (3), and the dihydroxy compound represented by general formula (4) is 5% or less of all components detected by the LC analysis.

[0009] (In general formulas (1), (2), and (4), R each independently represents a divalent group represented by general formula (1a) or (1b), and in general formulas (2) and (3), X each independently represents a halogen atom.) (In general formula (1a), R １ each independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, a phenyl group, a phenoxy group, or a phenylalkyl group having 7 to 10 carbon atoms; m represents 0 or an integer of 1 to 4; n represents 0 or 1; p and q represent 0, 1, or 2; and * represents each bonding position. (In general formula (1b), R １ and m are the same as defined in general formula (1a); Y represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group; Z represents an oxygen atom, a sulfur atom, or no bridge; each Ar independently represents an aryl group having 6 to 8 carbon atoms; and * represents a bonding position.

[0010] Liquid chromatography (LC) analysis of the aromatic ether nitrile composition (A) using ultraviolet light at a wavelength of 280 nm as a detector can be performed in detail by the method described in the Examples below. The lower limit of the numerical range of the composition (i) of the aromatic ether nitrile composition (A) is preferably 15% or more, more preferably 20% or more, and particularly preferably 30% or more, from the viewpoint of reducing melt viscosity and improving crystallinity. The upper limit of the numerical range of the composition (ii) of the aromatic ether nitrile composition (A) is preferably 3% or less, more preferably 2% or less, and particularly preferably 1% or less, from the viewpoint of suppressing weight loss at high temperatures during molding, i.e., gas generation. The lower limit of this numerical range is not limited, as the smaller the value, the better, but it may be 0.01% or more, and even more preferably 0.001% or more.

[0011] R in general formula (1a) １ each independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, a phenyl group, a phenoxy group, or a phenylalkyl group having 7 to 10 carbon atoms; a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 or 4 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a phenyl group is preferred; a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 or 4 carbon atoms, or a phenyl group is more preferred, and a methyl group is particularly preferred. Note that a "phenylalkyl group having 7 to 10 carbon atoms" refers to a group represented by a phenyl group and an alkylene group having 1 to 4 carbon atoms bonded to the phenyl group. An "alkylene group having 1 to 4 carbon atoms" refers to a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms. The alkylene group having 1 to 4 carbon atoms is preferably a methylene group or a branched alkylene group having 3 carbon atoms, and more preferably a methylene group or an isopropylidene group. In general formula (1a), m represents 0 or an integer of 1 to 4, preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0. In general formula (1a), n represents 0 or 1, and preferably 1. In general formula (1a), p and q each independently represent 0, 1, or 2, and preferably each independently represent 0 or 1, and particularly preferably 0. When n is 1 and p and q are 0, general formula (1a) is represented as general formula (1a'). (In the formula, R １ , m, and * are defined as in general formula (1a). In general formula (1a'), the bonding position indicated by * is preferably the ortho-position or para-position relative to the direct bonding position of the two benzene rings (i.e., 2,2-biphenylene group or 4,4-biphenylene group), and particularly preferably the para-position (i.e., 4,4-biphenylene group). R in general formula (1a') １ When m is 1 or 2, the bonding position of R is preferably the meta position with respect to the direct bonding position of the two benzene rings. １The preferred embodiments of n, p and q are the same as those in formula (1a). When n, p and q are 0, formula (1a) is represented by formula (1a''). (In the formula, R １ , m, and * are defined as in general formula (1a). In general formula (1a″), the bonding position indicated by * is preferably the para-position or meta-position relative to the other bonding position (i.e., a 1,4-phenylene group or a 1,3-phenylene group), and particularly preferably the para-position (i.e., a 1,4-phenylene group). R １ The preferred embodiments of n and q are the same as those in general formula (1a). When n and q are 0 and p is 1, general formula (1a) is represented as general formula (1a'''). (In the formula, R １ , m, and * are defined as in general formula (1a). In general formula (1a'''), the two bonding positions indicated by * are preferably the 1st and 5th positions, the 2nd and 6th positions, or the 2nd and 7th positions of the naphthalene ring (i.e., a 1,5-naphthylene group, a 2,6-naphthylene group, or a 2,7-naphthylene group), more preferably the 2nd and 6th positions, or the 2nd and 7th positions of the naphthalene ring (i.e., a 2,6-naphthylene group or a 2,7-naphthylene group), and particularly preferably the 2nd and 6th positions of the naphthalene ring (i.e., a 2,6-naphthylene group). R １ The preferred embodiments of R and m are the same as those in general formula (1a). １and m are the same as those defined in general formula (1a), and preferred embodiments are also the same. In general formula (1b), Y represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cyclic alkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group, and the cyclic alkylidene group having 5 to 15 carbon atoms may contain an alkyl group as a branched chain. Specific examples of the cyclic alkylidene group include a cyclopentylidene group (5 carbon atoms), a cyclohexylidene group (6 carbon atoms), a 3-methylcyclohexylidene group (7 carbon atoms), a 4-methylcyclohexylidene group (7 carbon atoms), a 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), a cycloheptylidene group (7 carbon atoms), and a cyclododecanylidene group (12 carbon atoms). Y in the general formula (1b) is preferably a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 6 carbon atoms, a fluorine-containing alkylidene group having 2 to 6 carbon atoms, a cyclic alkylidene group having 5 to 12 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group, and more preferably a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 3 carbon atoms, a fluorine-containing alkylidene group having 2 to 3 carbon atoms, a cyclic alkylidene group having 6 to 12 carbon atoms, a phenylmethylidene group, or a fluorenylidene group. A fluorenylidene group is more preferred, an alkylidene group having 3 carbon atoms, i.e., a propylidene group, a fluorine-containing alkylidene group having 3 carbon atoms, i.e., a fluorine-containing propylidene group, a cyclic alkylidene group having 6 to 12 carbon atoms, and a fluorenylidene group are even more preferred, and a 2,2-propylidene group, a 1,1,1,3,3,3-hexafluoro-2,2-propylidene group, a cyclohexylidene group, a 3,3,5-trimethylcyclohexylidene group, a cyclododecanylidene group, and a fluorenylidene group are particularly preferred. Z in general formula (1b) represents an oxygen atom, a sulfur atom, or no bridge, and is preferably an oxygen atom or no bridge, and more preferably no bridge. Ar in general formula (1b) represents an aryl group having 6 to 8 carbon atoms, and is more preferably a phenyl group.X in general formulas (2) and (3) each independently represent a halogen atom, preferably each independently represent a fluorine atom, chlorine atom, bromine atom, or iodine atom, more preferably each independently represent a fluorine atom or a chlorine atom, and particularly preferably both represent a chlorine atom. R in general formulas (1), (2), and (4) are preferably each not independently a divalent group represented by general formula (1a), more preferably each not independently a divalent group represented by general formula (1a'), a divalent group represented by general formula (1a''), or a divalent group represented by general formula (1a'''), further preferably each not independently a phenylene group, a naphthylene group, or a biphenylene group, even more preferably each not independently a 1,3-phenylene group, a 1,4-phenylene group, or a 4,4-biphenylene group, and particularly preferably each not independently a 4,4-biphenylene group. A particularly preferred embodiment of R in the general formulas (1), (2), and (4) where R is not independent and is a 4,4-biphenylene group will be specifically described. This means that groups corresponding to R are all 4,4-biphenylene groups, as in the compounds represented by the chemical formulas (1-1), (2-1), and (4-1) described below.

[0012] The aromatic ether nitrile composition (A) may contain, in addition to the compounds represented by the general formulae (1), (2), (3), and (4), a polymer having a repeating unit of the general formula (5) produced by the reaction of the compounds represented by the general formulae (3) and (4). (R in general formula (5) is common to general formulas (1), (2), and (4), and each independently represents a divalent group represented by general formula (1a) or general formula (1b).) There are no particular restrictions on the terminal structure of such a polymer. Both terminals may be hydroxy groups derived from the dihydroxy compound represented by general formula (4), which is the raw material, or both terminals may be halogen atoms derived from the dihalobenzonitrile compound represented by general formula (3), which is the raw material, or one terminal may be the hydroxy group and the other terminal may be the halogen atom. A preferred embodiment of R in general formula (5) is the same as R in general formulas (1), (2), and (4). A particularly preferred embodiment of R in general formula (5), in which R is not independent and is a 4,4-biphenylene group, will be specifically described. This means that, like the compounds represented by chemical formulae (1-1), (2-1), and (4-1) described below, and a polynuclear compound having a repeating unit represented by chemical formula (5-1), the groups corresponding to R are all 4,4-biphenylene groups.

[0013] The aromatic ether nitrile composition (A) of the present invention preferably has a weight average molecular weight (Mw) of 500 to 8,000 in terms of polystyrene as measured by gel permeation chromatography (GPC). If the weight average molecular weight (Mw) is 8,000 or more, a large amount may need to be added to the heat-resistant resin to achieve the effects of the present invention, which is not preferred. Furthermore, if the weight average molecular weight (Mw) is less than 500, the composition of the aromatic ether nitrile composition (A) of the present invention may deviate from the composition of the present invention. In order to achieve effects such as reduced melt viscosity with a small amount of the aromatic ether nitrile composition (A) of the present invention added to the heat-resistant resin, the weight average molecular weight (Mw) is more preferably in the range of 500 to 4,000, even more preferably in the range of 500 to 3,000, and particularly preferably in the range of 500 to 2,000.

[0014] <Aromatic Polyether Nitrile (B)> The aromatic polyether nitrile (B) of the present invention has a weight average molecular weight (Mw) of 50,000 or more in terms of polystyrene as measured by gel permeation chromatography analysis, and has a repeating unit represented by general formula (5). (R in general formula (5) is defined the same as in general formulas (1), (2), and (4).)

[0015] The aromatic polyethernitrile (B) has a weight average molecular weight (Mw) of 50,000 or more, as measured by gel permeation chromatography (GPC) analysis in terms of polystyrene, and if it is less than 50,000, the mechanical strength of the aromatic polyethernitrile resin composition of the present invention may be poor. Furthermore, since a large amount of the aromatic ethernitrile composition (A) is used to improve moldability, the weight average molecular weight (Mw) is preferably in the range of 50,000 to 1,000,000, more preferably 50,000 to 500,000, and particularly preferably 50,000 to 300,000. The preferred embodiments of R in the general formula (5) of the aromatic polyethernitrile (B) are the same as those in the general formulae (1), (2), and (4). R in the general formula (5) of the aromatic polyether nitrile (B) is common to the general formulae (1), (2), and (4) of the aromatic ether nitrile composition (A), and is preferably not independent and has the same definition as in the general formulae (1), (2), and (4). In this case, the particularly preferred embodiment of R in the general formula (5) of the aromatic polyether nitrile (B), in which R is not independent and is a 4,4-biphenylene group, will be specifically explained. This means that the groups corresponding to R are all 4,4-biphenylene groups, as in the compounds represented by the chemical formulae (1-1), (2-1), and (4-1) contained as the aromatic ether nitrile composition (A), which will be described later.

[0016] (Method for Producing Aromatic Ethernitrile Composition (A) of the Present Invention) The aromatic ethernitrile composition (A) of the present invention can be produced by a method comprising: an etherification reaction step in which a dihalobenzonitrile compound represented by the general formula (3), a dihydroxy compound represented by the general formula (4), and a basic compound that forms a salt with the hydroxyl group of the dihydroxy compound represented by the general formula (4) are reacted to obtain a reaction product containing the compound represented by the general formula (1); and an alkali washing step in which the reaction product obtained by the etherification reaction step is washed with an aqueous solution of a basic compound, wherein the dihydroxy compound represented by the general formula (4) is used in an amount of 1.5 times or more by mole relative to the dihalobenzonitrile compound represented by the general formula (3), and the basic compound that forms a salt with the terminal hydroxyl group of the dihydroxy compound represented by the general formula (4) is used in an amount of 2 times or more by mole relative to the dihydroxy compound represented by the general formula (4).

[0017] The dihydroxy compound represented by general formula (1) is produced by the following reaction between a dihalobenzonitrile compound represented by general formula (3) and two moles of the dihydroxy compound represented by general formula (4) in the presence of a basic compound that forms a salt with the hydroxyl group of the dihydroxy compound represented by general formula (4): The compound represented by general formula (2) is produced by the reaction between a dihalobenzonitrile compound represented by general formula (3) and one mole of the dihydroxy compound represented by general formula (4): Alternatively, in the etherification reaction step, a salt of the dihydroxy compound of general formula (4) formed by salting the hydroxyl group of the dihydroxy compound represented by general formula (4) with a basic compound may be synthesized in advance, and the salt may then be reacted with the dihalobenzonitrile compound of general formula (3). Since the above reaction involves a reaction between bifunctional monomers, a polymerization reaction also occurs in parallel, resulting in a composition containing not only the dihydroxy compound of general formula (1) but also compounds with lower and higher molecular weights. During the desalting reaction, water is generated, but this water may or may not be removed from the system. For example, the reaction may be carried out in the presence of a solvent that forms an azeotrope with water at a temperature at which the desalting reaction proceeds. During this time, water may be distilled off from the reaction mixture using a solvent that forms an azeotrope with water, or the azeotrope may be refluxed as is. The temperature at which the desalting reaction begins is usually around 130°C, depending on the raw materials. For example, when 4,4'-biphenol is used as the dihydroxy compound of general formula (4) and 2,6-dichlorobenzonitrile is used as the dihalobenzonitrile compound of general formula (3), potassium carbonate, sulfolane (boiling point 285°C) as the aprotic solvent, and toluene as the solvent that forms an azeotrope with water, the reaction temperature is preferably in the range of 130 to 170°C. The reaction is carried out in an inert atmosphere, for example, in a nitrogen atmosphere, at atmospheric pressure, but may also be carried out under elevated or reduced pressure.

[0018] <Dihydroxy Compound Represented by General Formula (4)> Specific examples of the dihydroxy compound represented by general formula (4) used as a component of the aromatic ether nitrile composition (A) of the present invention or a raw material for producing the same include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4'-biphenol, 3,3'-biphenol, 2,2'-biphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,1'-bi-2-naphthol, 2,2'-bi-1-naphthol, 1,3-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene ... ,4-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,3-(4-hydroxybenzoylbenzene), 1,4-(4-hydroxybenzoylbenzene), 1,3-bis(4-hydroxyphenoxy)benzene, 1,4-bis(4-hydroxyphenoxy)benzene, 1,4-bis(4-hydroxyphenyl)benzene, 1,3-bis(4-hydroxyphenyl)benzene, 4,4'-isopropylidenebiphenol (Bis-A), 2,2-bis(4-hydroxyphenyl)-1,1,1,3, 3,3-hexafluoropropane, 4,4'-bishydroxybenzophenone, 4,4'-bishydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)methane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-phenyl-4-hydroxyphenyl)fluorene, 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy 1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol TMC (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and the like.Among these, hydroquinone, resorcinol, and 4,4'-biphenol are preferred, with 4,4'-biphenol being particularly preferred.

[0019] <Dihalobenzonitrile Compound Represented by General Formula (3)> Specific examples of the dihalobenzonitrile compound represented by general formula (3) used as a component of the aromatic ether nitrile composition (A) of the present invention or a raw material for producing the same include 2,6-difluorobenzonitrile, 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, 2,6-dibromobenzonitrile, 2,5-dibromobenzonitrile, 2,4-dibromobenzonitrile, 2,6-dinitrobenzonitrile, 2,5-dinitrobenzonitrile, 2,4-dinitrobenzonitrile, and 1,4-dichloro-2,5-dicyanobenzene. In the etherification reaction step, in addition to the dihalobenzonitrile compound represented by general formula (3), reactive derivatives of these compounds may also be included. The reactive derivative is a compound that can react with a dihydroxy compound represented by general formula (1) or (4), such as a structure derived from 2,6-dihalobenzonitrile, as represented by the following formula, and means a compound derived by reacting two 2,6-dihalobenzonitriles or a 2,6-dihalobenzonitrile with a dihydroxy compound represented by general formula (4). (In the formula, R is defined as in general formula (4), and X is defined as in general formula (3). Among these, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity, economy, etc. Two or more of these compounds can also be used in combination.

[0020] <Amount of Raw Material Used> In the production method of the present invention, the dihydroxy compound represented by general formula (4) is preferably used in an amount of 1.5 or more times by mole relative to the dihalobenzonitrile compound represented by general formula (3), and from the viewpoint of efficient use of raw materials, it is more preferably used in an amount of 1.5 to 10 times by mole, even more preferably used in an amount of 1.5 to 5 times by mole, and particularly preferably used in an amount of 1.5 to 3 times by mole. In the etherification reaction step, in order to maximize the selectivity of the compound represented by general formula (1), it is suitable to use the dihydroxy compound represented by general formula (4) in an amount of 2 times by mole relative to the dihalobenzonitrile compound represented by general formula (3).

[0021] <Basic Compound> The basic compound may be any compound, whether organic or inorganic, that promotes the desalting polycondensation reaction and does not affect the quality. Of the organic and inorganic basic compounds, inorganic basic compounds are preferred, and among these, alkali metal compounds and alkaline earth metal compounds are more preferred, with alkali metal compounds being particularly preferred. Examples of organic basic compounds include tetramethylammonium hydroxide, triethylamine, N,N-diisopropylethylamine, 1,1,3,3-tetramethylguanidine (TMG), N,N-dimethyl-4-aminopyridine (DMAP), 2,6-lutidine, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD). Diazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-bis(dimethylaminonaphthalene) (DMAN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tert-butylimino-tri(pyrrolidino)phosphorane, tert-butylimino-tris(dimethylamino)phosphorane, 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine, tert-octylimino-tris(dimethylamino)phosphorane, phosphazene base P ２ -Et, phosphazene base P ２-t-Bu, phosphazene base P ３ -t-Bu, phosphazene base P ４ -t-Bu, phosphazene base P ４ -t-Oct. Among the inorganic base compounds, examples of alkali metal compounds include alkali metals such as lithium, rubidium, cesium, potassium, and sodium; alkali metal hydrides such as lithium hydride, rubidium hydride, cesium hydride, potassium hydride, and sodium hydride; alkali metal hydroxides such as lithium hydroxide, rubidium hydroxide, cesium hydroxide, potassium hydroxide, and sodium hydroxide; alkali metal carbonates such as lithium carbonate, rubidium carbonate, cesium carbonate, potassium carbonate, and sodium carbonate; and alkali metal bicarbonates such as lithium bicarbonate, rubidium bicarbonate, cesium bicarbonate, potassium bicarbonate, and sodium bicarbonate. These compounds can be used alone or in combination of two or more. The specific surface area of ​​these alkali metal compounds is 0.3 m or less. ２ By using an alkali metal compound catalyst having a specific surface area of ​​0.8 m / g or more, the desalination polycondensation reaction can be carried out with high efficiency. ２ / g or more, and 1.2m ２ / g or more is more preferable. By using an alkali metal compound with a larger specific surface area, the contact opportunity between the catalyst and the reaction raw materials increases, and it becomes possible to carry out the desalination polycondensation reaction with even higher efficiency. ２ When the specific surface area is less than 0.3 m / g, the desalting polycondensation reaction cannot be carried out with sufficiently high efficiency unless the amount of catalyst is increased, but increasing the amount of catalyst is not preferred because it affects the quality of the polymer. From the above, the basic compound in the production method of the present invention is preferably an alkali metal carbonate such as lithium carbonate, rubidium carbonate, cesium carbonate, potassium carbonate, or sodium carbonate, more preferably lithium carbonate, potassium carbonate, or sodium carbonate, and particularly preferably a basic compound having a specific surface area of ​​0.3 m / g from the viewpoint of availability. ２The amount of the basic compound used in the production method of the present invention is, for example, in the case of an alkali metal compound, 2 or more times by mole the amount of alkali metal ions contained in the dihydroxy compound represented by general formula (4). However, if used in large excess, side reactions such as cleavage of ether bonds occur during polymerization, so the range of 2 to 4 times by mole is more preferable, the range of 2 to 2.4 times by mole is even more preferable, and the range of 2 to 2.2 times by mole is particularly preferable.

[0022] <Solvent> In the etherification reaction step in the method for producing the aromatic ether nitrile composition (A) of the present invention, a reaction solvent can be used, and it is preferable to use an aprotic solvent as the reaction solvent. Specific examples of aprotic solvents include N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzenes (alkoxy groups having 1 to 4 carbon atoms), and trialkoxybenzenes (alkoxy groups having 1 to 4 carbon atoms). Among these solvents, polar organic solvents with high dielectric constants, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, sulfolane, diphenyl sulfone, and dimethyl sulfoxide, are particularly preferred. These solvents can be used alone or in combination of two or more. The amount of aprotic solvent used is not particularly limited, as long as it uniformly dissolves the raw materials and satisfactorily disperses the alkali metal salt. It is sufficient to select an amount that maximizes the volumetric efficiency of the polymerization vessel relative to the raw materials used and the target composition. Typically, the amount is selected within a range of 0.5 to 20 times the total weight of the raw materials and the alkali metal salt. Specific examples of solvents that form an azeotrope with water include aromatic hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole. These solvents may be used alone or in combination of two or more. When a solvent that forms an azeotrope with water is used, it is preferable to use 1 to 100 parts by weight of the solvent that forms an azeotrope with water per 100 parts by weight of the aprotic solvent. From the viewpoints of volumetric efficiency and solvent recovery, a range of 1 to 10 parts by weight is more preferable, and a range of 2 to 5 parts by weight is even more preferable.

[0023] <Reaction Temperature> The reaction temperature in the etherification reaction step is preferably in the range of 140 to 200°C, more preferably in the range of 150 to 170°C, and even more preferably in the range of 155 to 165°C.

[0024] <Reaction Time> The reaction time for the etherification reaction step varies depending on the reaction conditions and the raw materials used, but is typically 3 to 20 hours. The reaction time is preferably continued until the amounts of the compounds represented by general formulas (2), (3), and (4) are minimized, but is not particularly limited. For example, when 2 moles of 4,4'-biphenol and 1 mole of 2,6-dichlorobenzonitrile are reacted at 160°C using 2 moles of potassium carbonate, sulfolane as an aprotic solvent, and toluene as a solvent that forms an azeotrope with water, all of the 2,6-dichlorobenzonitrile corresponding to the dihalobenzonitrile compound represented by general formula (3) is consumed within 4 hours, and the compound represented by chemical formula (2-1) described below, which corresponds to the compound represented by general formula (2), is produced in an amount of about 20% within 1 hour after the start of the reaction, but this amount decreases as the reaction time elapses and is completely consumed after 8 hours, reaching a maximum amount of the compound corresponding to general formula (1).

[0025] (Treatment after Etherification Reaction Step) After the etherification reaction step is completed, the reaction product is extracted from the reactor, cooled and solidified, and then pulverized to be subjected to the subsequent alkali washing step. Alternatively, the reaction product extracted from the reactor may be directly charged into a washing tank for the alkali washing step. Alternatively, a solvent to be used in the alkali washing step described below may be injected into the reactor after the reaction is completed, and the reaction product may be transferred to the alkali washing step in the form of a slurry or wax.

[0026] The alkali washing step is a washing step for removing the salts and reaction solvent contained in the reaction product obtained in the etherification reaction step, as well as the remaining dihydroxy compound of general formula (4). Prior to this alkali washing step, the reaction solvent in the reaction product is preferably extracted and washed using a solvent such as an alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, or water, and then the salts formed by the desalting reaction in the reaction product are preferably washed and removed using water. After removing the solvent and salt, the remaining dihydroxy compound of general formula (4) is removed using an aqueous solution of a basic compound. The washing is then completed by neutralization with an acid or an aqueous solution thereof. Specifically, the reaction product in a pulverized, slurry, or waxy state is transferred to a container equipped with a stirrer, and the stirring, washing, and filtration procedures with a washing solvent are repeated until the reaction solvent, salt, and dihydroxy compound of general formula (4) are reduced to or below the target content. As the apparatus, a washing tank and a pressure filter or a centrifuge, as well as a multifunctional filter capable of washing, filtration, and drying in one device, may be used. Specific examples of the extraction and washing solvent for the reaction solvent other than water include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, t-amyl alcohol, n-hexyl alcohol, cyclohexanol, n-octyl alcohol, capryl alcohol, etc. Specific examples of ketones include acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, 2-hexanone, 3-hexanone, methyl-t-butyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, di-n-amyl ketone, diacetyl, acetylacetone, cyclohexanone, benzophenone, etc.Examples of aliphatic hydrocarbons include saturated aliphatic hydrocarbons such as n-hexane, 2-methylheptane, 3-methylheptane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, and cyclohexane; and unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene, and cyclohexene. Examples of aromatic hydrocarbons include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, t-butylbenzene, styrene, and allylbenzene. Among these, methanol, ethanol, acetone, methyl ethyl ketone, xylene, and toluene are preferred, with acetone and methanol being particularly preferred from the viewpoints of operability and ease of distillation recovery of the reaction solvent after washing. Water is preferred for washing alkali metal salts such as potassium chloride produced in the desalting condensation reaction, but acidic water containing low concentrations of hydrochloric acid, oxalic acid, or acetic acid may also be used. The basic compound used in the aqueous solution of basic compounds for removing the remaining dihydroxy compound represented by general formula (4) is preferably the basic compound described in the etherification reaction step. The concentration of the aqueous solution of basic compounds is preferably several percent to 10%. From a cost perspective, an aqueous solution of sodium hydroxide or potassium hydroxide is preferred. After removing the dihydroxy compound represented by general formula (4) in the alkali washing step, the excess basic compound is neutralized with acidic water containing hydrochloric acid, oxalic acid, or acetic acid, and the excess acidic compound is removed with water to complete the washing operation. The conditions for this washing step, such as the amount of washing solvent used, the number of washes, and the washing temperature, can be appropriately selected depending on the amounts of residual reaction solvent, residual salt, and remaining dihydroxy compound of general formula (4) to be removed.

[0027] The drying step is a step of drying the composition obtained in the washing step. The composition containing water after washing is dried by a known method. Known devices such as an evaporator, a tray oven, or a tumbler can be used as the dryer. The target water content is usually 0.5% by weight or less, preferably 0.4% by weight or less, and more preferably 0.3% by weight or less. The conditions for this drying step may be any conditions that allow removal of water at a temperature below the melting point of the composition. To minimize contact with air, the drying step is preferably carried out in an inert gas (nitrogen, argon, etc.) atmosphere, in an inert gas stream, or under reduced pressure.

[0028] (Method for Producing Aromatic Polyethernitrile (B) of the Present Invention) The aromatic polyethernitrile (B) of the present invention can be obtained by polycondensation of a dihalobenzonitrile compound represented by the general formula (3) with a dihydroxy compound represented by the general formula (4) in the presence of a basic compound that forms a salt with the hydroxyl group of the dihydroxy compound represented by the general formula (4) to obtain an aromatic polyethernitrile having a repeating unit represented by the general formula (5). The reaction formula in this case is shown below. Alternatively, a salt of the dihydroxy compound of general formula (4) may be synthesized in advance by forming a salt with the hydroxyl group of the dihydroxy compound of general formula (4) using a basic compound, and then the polycondensation reaction may be carried out using the salt and the dihalobenzonitrile compound of general formula (3).

[0029] In the production of the aromatic polyether nitrile (B) according to the present invention, the molar ratio of the dihydroxy compound represented by the general formula (4) to the dihalobenzonitrile compound represented by the general formula (3) can be set arbitrarily depending on the target molecular weight, but when it is desired to obtain an aromatic polyether nitrile having a repeating unit represented by the general formula (5) with a weight average molecular weight (Mw) of 50,000 or more, the molar ratio is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.95 to 1.05, and particularly preferably in the range of 0.99 to 1.01. In order to maximize the polymerization rate of the polycondensation reaction, it is preferable to use the dihydroxy compound represented by the general formula (4) and the dihalobenzonitrile compound represented by the general formula (3) at a molar ratio of substantially 1.00.

[0030] The preferred types and amounts of the basic compound and reaction solvent used in the polycondensation reaction are as explained in the method for producing an aromatic ether nitrile composition.

[0031] (Polycondensation Reaction Method) The polycondensation reaction to obtain the aromatic polyether nitrile (B) may be carried out by dividing it into an oligomer formation step (1) and a polymerization step (2), each using a different reaction method, or it may be carried out without dividing the steps. The oligomer formation step (1) is a step in which a dihydroxy compound represented by general formula (4) and a dihalobenzonitrile compound represented by general formula (3) are polycondensed in the presence of a basic compound to form an oligomer. The oligomer referred to here is not particularly limited, but a polycondensation reaction product in which the weight-average molecular weight of the polymer is approximately less than 30,000 is referred to as an oligomer. The polymerization step (2) is a step in which the oligomer obtained in step (1) is further polycondensed to form a polymer. In this case, the polycondensation reaction solution of step (1) can be used as is, or an oligomer isolated by separately carrying out step (1) can also be used.

[0032] The polycondensation reaction to obtain the aromatic polyether nitrile (B) according to the present invention includes an operation for removing water generated during the desalting reaction from the system. Examples of such an operation include carrying out the reaction in the presence of a solvent that forms an azeotrope with water at a temperature at which the desalting reaction proceeds, and during this time, removing water by distillation from the reaction mixture using a solvent that forms an azeotrope with water. This allows the reaction to be maintained in a substantially anhydrous state. The temperature at which the desalting reaction begins is typically around 130°C, although this depends on the raw materials. For example, when 4,4'-biphenol is used as the dihydroxy compound represented by general formula (4), 2,6-dichlorobenzonitrile is used as the dihalobenzonitrile compound represented by general formula (3), potassium carbonate is used, sulfolane (boiling point 285°C) is used as the aprotic solvent, and toluene is used as the solvent that forms an azeotrope with water, a reaction temperature in the range of 130 to 170°C is preferred. Specific examples of the solvent that forms an azeotrope with water include aromatic hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole. These can be used alone or in combination of two or more. When using a solvent that forms an azeotrope with water, it is preferable to use 1 to 100 parts by weight of the solvent that forms an azeotrope with water per 100 parts by weight of the aprotic solvent. From the viewpoints of volumetric efficiency and solvent recovery, a range of 1 to 10 parts by weight is more preferable, and a range of 2 to 5 parts by weight is even more preferable.

[0033] When the reaction is continued, it is preferable to maintain the reaction system in a substantially anhydrous state while removing the water generated by the reaction. If the generated water is not sufficiently removed, the water reacts with the dihalobenzonitrile compound represented by general formula (3) to form a by-product having a phenol skeleton, resulting in the production of only a low molecular weight product. That is, in order to obtain a high molecular weight polyether nitrile, it is preferable to keep the reaction system substantially anhydrous, preferably less than 0.5 wt %.

[0034] <Polycondensation Reaction Conditions> The temperature of the polycondensation reaction to obtain the aromatic polyether nitrile (B) is in the range of 140 to 300°C. Within this range, the reaction may be continued at a constant temperature, or the reaction temperature may be increased as the polycondensation reaction progresses. When the polycondensation reaction is carried out in two separate steps, an oligomer formation step (1) and a polymerization step (2), the reaction temperature of the oligomer formation step (1) is preferably in the range of 140 to 200°C, more preferably in the range of 150 to 170°C, and even more preferably in the range of 155 to 165°C. The reaction temperature of the polymerization step (2) is preferably in the range of 190 to 300°C, more preferably in the range of 210 to 270°C, even more preferably in the range of 210 to 240°C, and particularly preferably in the range of 215 to 230°C. For example, when 4,4'-biphenol is used as the dihydroxy compound represented by general formula (4), 2,6-dichlorobenzonitrile is used as the dihalobenzonitrile compound represented by general formula (3), potassium carbonate, sulfolane (boiling point 285°C) as the aprotic solvent, and toluene as the solvent that forms an azeotrope with water, a temperature range of 190 to 280°C is preferred. The pressure for the polycondensation reaction may be normal pressure, or a higher or lower pressure. The polycondensation reaction is preferably carried out in an inert atmosphere, for example, in a nitrogen atmosphere, or at atmospheric pressure.

[0035] The reaction time for the polycondensation reaction to obtain the aromatic polyether nitrile (B) according to the present invention depends on the molar ratio of the dihydroxy compound represented by the general formula (4) to the dihalobenzonitrile compound represented by the general formula (3) and the amount of the basic compound used, and can be arbitrarily set depending on the molecular weight of the targeted polyether nitrile, but is usually 3 to 20 hours.

[0036] <Post-Reaction Treatment> After the polycondensation reaction of the aromatic polyether nitrile (B) is completed, the following treatment is preferably carried out: The polycondensation reaction product is withdrawn from the reactor, cooled and solidified, and then pulverized to be subjected to the subsequent washing step, drying step, and step of producing a molding material (pellets, chips), or the polycondensation reaction product withdrawn from the reactor may be directly charged into a washing tank in the washing step, or a solvent to be used in the washing step described below may be poured into the reactor after the polycondensation reaction is completed, and the product may be transferred to the washing step in the form of a slurry or wax.

[0037] The washing step is a step for removing salts, reaction solvents, and the like contained in the polycondensation reaction product obtained by the polycondensation reaction. This washing step is preferably carried out by a known method, using a solvent such as an alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, or water to extract and wash the reaction solvent from the polycondensation reaction product, and then preferably using water to wash and remove salts generated by the desalting reaction in the polycondensation reaction product. Specifically, the polycondensation reaction product in a pulverized, slurry, or waxy state is transferred to a container equipped with a stirrer, and the operations of stirring and washing with a washing solvent and filtration are repeated until the reaction solvent and salt content are reduced to or below the target levels. As the apparatus, a washing tank and a pressure filter or a centrifuge, as well as a multifunctional filter capable of washing, filtration, and drying in one device, may be used. Specific examples of the extraction and washing solvent for the reaction solvent other than water include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, t-amyl alcohol, n-hexyl alcohol, cyclohexanol, n-octyl alcohol, capryl alcohol, etc. Specific examples of ketones include acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, 2-hexanone, 3-hexanone, methyl-t-butyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, di-n-amyl ketone, diacetyl, acetylacetone, cyclohexanone, benzophenone, etc. Examples of aliphatic hydrocarbons include saturated aliphatic hydrocarbons such as n-hexane, 2-methylheptane, 3-methylheptane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, and cyclohexane; and unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene, and cyclohexene.Examples of aromatic hydrocarbons include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, t-butylbenzene, styrene, and allylbenzene. Among these, methanol, ethanol, acetone, methyl ethyl ketone, xylene, and toluene are preferred, with acetone and methanol being particularly preferred due to their ease of operation and ease of distillation recovery of the reaction solvent after washing. Water is preferred for washing alkali metal salts such as potassium chloride produced in the desalting polycondensation reaction, and acidic water containing low concentrations of oxalic acid or acetic acid may also be used. Conditions for this washing step may be appropriately selected, such as the amount of washing solvent used, the number of washes, and the washing temperature, depending on the amounts of residual reaction solvent and residual alkali metal salts to be removed.

[0038] The drying step is a step of drying the polycondensation reaction product that has been subjected to the above-mentioned washing step. The polycondensation reaction product containing moisture after washing is dried by a known method. Known devices such as an evaporator, a tray oven, or a tumbler can be used as the dryer. The target moisture content is usually 0.5% by weight or less, preferably 0.4% by weight or less, and more preferably 0.3% by weight or less. The conditions for this drying step may be any conditions that allow moisture removal at a temperature below the melting point of the polycondensation reaction product. To minimize contact with air, the drying step is preferably carried out under an inert gas (nitrogen, argon, etc.) atmosphere, under an inert gas stream, or under reduced pressure. The dried polycondensation reaction product is basically a powder.

[0039] The aromatic polyethernitrile (B) according to the present invention may be in the form of a molding material (pellets, chips, etc.) for producing a molded article of aromatic polyethernitrile. There are no particular limitations on the method for producing such a molding material; however, the powdered aromatic polyethernitrile obtained as described above may be heated and melted and molded into a molding material shape such as pellets or chips. The heating, melting, and molding operations are preferably carried out under an oxygen-shielded or inert atmosphere such as nitrogen. Typically, a melt-kneading device such as a single-screw, twin-screw, or multi-screw extruder, a Banbury mixer, a kneader, or a roller is used to produce molding materials such as pellets or chips. However, a sheet produced using a compression molding machine may be cut to produce molding materials such as pellets or chips. The industrially preferred process for producing molding materials is as follows: The aromatic polyethernitrile powder that has been polycondensed, pulverized, washed, and vacuum-dried is directly transferred and stored in a silo sealed with nitrogen gas or the like without being exposed to the outside air. When molding into pellets, chips, etc., it is transferred directly through a pipe to an extruder together with nitrogen gas. The resulting mixture is melt-kneaded without contact with oxygen (air), and the molten polymer from the die is pelletized by underwater cutting or water-cooled cutting of strands. The conditions for the manufacturing process of this molding material (pellets, chips) are melt processing conditions, in which the above operations are carried out at a temperature sufficient to melt the polymer. The upper limit of the melt processing temperature is 500°C or less. The aromatic polyether nitrile (B) obtained using biphenol and 2,6-dichlorobenzonitrile used in the examples had a melting point of about 345°C, so it is preferable to process at a higher temperature, 360°C or more. The upper limit of the temperature is preferably 480°C or less, more preferably 450°C or less, even more preferably 430°C or less, and particularly preferably 400°C or less.

[0040] <Method for producing aromatic polyether nitrile resin composition> The method for producing the aromatic polyether nitrile resin composition of the present invention is not particularly limited, but may be carried out by mixing the aromatic ether nitrile composition (A) and the aromatic polyether nitrile (B) obtained as described above by a known method, and melt-kneading the mixture using the above-mentioned method for producing a molding material (pellets, chips, etc.) of the aromatic polyether nitrile (B), i.e., using a single-screw, twin-screw, or multi-screw extruder, a Banbury mixer, a kneader, a roller, or the like to produce a molding material such as pellets or chips, thereby producing a highly heat-resistant resin composition which generates little gas, has high melt fluidity, a high crystallization rate, and has improved moldability. The weight ratio (A) / (B) of the aromatic ether nitrile composition (A) to the aromatic polyether nitrile (B) is preferably in the range of 1 / 99 to 50 / 50, and in view of the balance between fluidity, heat resistance, and crystallization rate, the weight ratio (A) / (B) is more preferably in the range of 10 / 90 to 40 / 60, still more preferably in the range of 15 / 85 to 35 / 65, and particularly preferably in the range of 20 / 80 to 35 / 65.

[0041] The aromatic polyethernitrile resin composition of the present invention can be used as a molding material by the above-mentioned method, or can be used to produce molded articles and parts, and has heat resistance, chemical resistance, flame retardancy, and high mechanical properties. For example, it can be used in electrical and electronic applications such as personal computers and semiconductor parts, automotive applications such as gears, bearings, and engine housings, medical devices, and aerospace applications.

[0042] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0043] The analytical methods used in the present invention are as follows. <Analytical Methods> (1) Compositional Analysis of Aromatic Ethernitrile Composition and Each Compound The obtained aromatic ethernitrile composition and the compound represented by the following chemical formula in each compound were quantified by dissolving a sample in tetrahydrofuran (THF) solvent and subjecting it to high performance liquid chromatography (HPLC) using the following equipment and conditions, based on the area ratio detected at a wavelength of 280 nm. The compound represented by chemical formula (5-1) is a polymer having the repeating unit. Apparatus: Ultra-high performance liquid chromatograph (UFLC) manufactured by Shimadzu Corporation Detector: UV [Measurement conditions] Column: HALO (registered trademark) 90A, C18 manufactured by Shimadzu GLC Corporation Flow rate: 0.8 mL / min Eluent: 0.1% aqueous phosphoric acid solution Tetrahydrofuran (THF) Temperature: 50°C Detection wavelength: 280 nm (2) Molecular weight measurement The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained aromatic ether nitrile composition, compound, aromatic polyether nitrile, and aromatic polyether nitrile resin composition were measured by diluting a 1% p-chlorophenol solution of the sample 10 times with chloroform, and measuring the solution using the apparatus and conditions described below. From this value, the molecular weight distribution Mw / Mn was calculated. Apparatus: Gel permeation chromatography: 515 HPLC pump, 717plus automatic injection device, 2487 ultraviolet-visible detector (manufactured by Nihon Waters K.K.) Column: 2 × PLgel 5 μ MIXED-D, 7.5 × 300 mm (manufactured by Agilent Technologies Inc.) Column temperature: 40 ° C. Flow rate: 1.0 mL / min Injection amount: 2.5 μL Detection: ultraviolet-visible detector: 254 nm Column calibration: monodisperse polystyrene (EasiCal PS-1 manufactured by Agilent Technologies Inc.) Molecular weight calibration: relative calibration method (polystyrene equivalent) Analysis software: Empower3 (manufactured by Nihon Waters K.K.) (3) Glass transition temperature (Tg) Using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60), the glass transition temperature (Tg) of the obtained aromatic polyether nitrile resin composition and aromatic polyether nitrile was measured under the following conditions. <Conditions> Sample: 10 mg Nitrogen flow rate: 50 mL / min Temperature change range: 50 to 370°C Temperature change rate: 10°C / min (4) 1% weight loss temperature (Td1) The 1% weight loss temperature (Td1) of the obtained aromatic polyether nitrile resin composition and aromatic polyether nitrile was measured under the following conditions using DTG NEXTA STA manufactured by Hitachi High-Tech Science Corporation.Sample: 10 mg Nitrogen flow rate: 100 mL / min. Temperature change range: 30 to 550°C Heating rate: 10°C / min. Sampling interval: 0.5 seconds (5) Measurement of crystallinity The crystallinity of the aromatic polyether nitrile and the aromatic polyether nitrile resin composition was calculated from the calorific value determined from the DSC measurement in the above analysis method (3) using the following formula: Crystallinity (%) = (heat of fusion - heat of recrystallization) / heat of fusion of perfect crystal × 100 The following value was used for the heat of fusion of perfect crystal. Aromatic polyether nitrile according to the present invention: 139 J / g, Standard PEEK resin (PEEK450G manufactured by Victrex): 130 J / g The heat of fusion of the completely crystalline aromatic polyether nitrile of the example was calculated from the crystallinity (22.4%) calculated by X-ray diffraction (XRD) of a sample prepared by melting the resin obtained in Example 2 at 380°C and then holding it at 200°C for 5 minutes to crystallize it, and the heat of recrystallization (0.0 J / g) and heat of fusion (31.2 J / g) determined by DSC measurement, according to the following formula: Heat of fusion of perfectly crystalline PEEK (J / g) = (heat of fusion - heat of recrystallization) / (XRD crystallinity) × 100 = (31.2 J / g - 0.0 J / g) / 22.4 × 100 = 139 J / g. The literature value (Polymer Handbook 4th Edition) was used for the heat of fusion of perfectly crystalline PEEK.

[0044] Synthesis Example 1 A four-necked, 3-liter reaction vessel equipped with a mechanical stirrer, a thermometer, a dry nitrogen inlet, and a reflux condenser was charged with 149.23 g (0.868 mol) of 2,6-dichlorobenzonitrile (hereinafter referred to as "DCBN"; purity determined by high-performance liquid chromatography was 99.90% by weight; the same applies hereinafter) as compound (3-1), 323.08 g (1.735 mol) of 4,4'-biphenol (hereinafter referred to as "BP"; purity determined by high-performance liquid chromatography was 99.95% by weight), 239.79 g (1.735 mol; 1.00 times the molar equivalent of BP) of anhydrous potassium carbonate, 60 g of toluene, and 1,562 g of anhydrous sulfolane. This mixture was heated from room temperature in a nitrogen stream and, while stirring at 250 rpm, heated to 160°C under reflux. At temperatures above 130°C, carbon dioxide was generated from the reaction of potassium carbonate and BP. The reaction was allowed to proceed while refluxing toluene and the generated water at 160 ° C., and after 8 hours, the reaction product was extracted from the bottom of the reaction vessel and allowed to cool and solidify. HPLC analysis confirmed that the compound (2-1) and the raw material DCBN were undetectable in the solidified product, and 19.2% of the raw material BP remained. This solidified product was washed with 2.5 times the weight of water and filtered three times, then washed with 1.5 times the weight of a 4 wt% aqueous solution of sodium hydroxide and filtered four times, and HPLC showed that the BP had decreased to less than 1%. Thereafter, the solidified product was washed with 1.5 times the weight of 4 wt% hydrochloric acid, filtered, washed with 1.5 times the weight of water, filtered three times, and dried at 120 ° C. for 5 hours under nitrogen to obtain 197 g of a white powder (hereinafter referred to as "aromatic ether nitrile composition α"). The potassium and sodium contents of aromatic ether nitrile composition α were each 10 ppm or less. The results of the composition and molecular weight of the aromatic ether nitrile composition α obtained by the above analytical methods are shown in Table 1.

[0045] Synthesis Example 2 A solidified product was obtained in the same manner as in Synthesis Example 1, except that the amount of DCBN was 298.45 g (1.735 mol), the amount of anhydrous potassium carbonate was 143.87 g (1.041 mol: 0.60 times the molar ratio of BP), and the reaction was carried out at 160°C for 5 hours. HPLC analysis confirmed that the solidified product contained 26.8% of compound (2-1), undetectable % of the raw material DCBN, and 10.8% of the raw material BP. This solidified product was subjected to the same procedure as in Synthesis Example 1 to obtain 328 g of a white powder (hereinafter referred to as the "comparative aromatic ether nitrile composition"). The potassium and sodium contents of the comparative aromatic ether nitrile composition were each 10 ppm or less. The composition and molecular weight of the comparative aromatic ether nitrile composition, as determined by the above analytical methods, are shown in Table 1.

[0046] Synthesis Example 3 A four-necked, 3-liter reaction vessel equipped with a mechanical stirrer, a thermometer, a dry nitrogen inlet, and a reflux condenser was charged with 149.23 g (0.868 mol) of DCBN, 295.48 g (1.735 mol) of 4-phenylphenol (hereinafter referred to as "PPP"; a reagent manufactured by Tokyo Chemical Industry Co., Ltd. with a gas chromatography purity of 99% or higher), 143.877 g (1.041 mol: 0.60 times the molar ratio of PPP), 60 g of toluene, and 1562 g of anhydrous sulfolane. This mixture was heated from room temperature in a nitrogen stream and, while stirring at 250 rpm, heated to 160°C under reflux. At temperatures above 130°C, carbon dioxide was generated from the reaction of potassium carbonate and PPP. The reaction was continued at 160°C while refluxing the toluene and the generated water. After 9 hours, the reaction product was withdrawn from the bottom of the reaction vessel and allowed to cool and solidify. This solidified product was washed with 2.5 times its weight of water and filtered three times, then washed with 1.5 times its weight of methanol and filtered three times, and dried at 120°C for 5 hours in nitrogen to obtain 433 g of a white powder of a compound represented by chemical formula (6) (compound (6)) with a purity of 98.3%. The potassium and sodium contents of the obtained compound (6) were each 10 ppm or less. The composition and molecular weight of the obtained compound (6) obtained by the above analytical methods are shown in Table 1.

[0047] Synthesis Example 4: A four-necked, 3-liter reaction vessel equipped with a mechanical stirrer, a thermometer, a dry nitrogen inlet, and a reflux condenser was charged with 298.45 g (1.735 mol) of DCBN, 323.08 g (1.735 mol) of BP, 251.79 g (1.822 mol; 1.05 times the molar ratio of BP) of anhydrous potassium carbonate, 60 g of toluene, and 1,562 g of anhydrous sulfolane. This mixture was heated from room temperature to 160°C under reflux while stirring at 250 rpm in a nitrogen stream. At temperatures above 130°C, carbon dioxide was generated from the reaction of potassium carbonate and BP. After 3 hours at 160°C, the oligomerization reaction between DCBN and BP was completed. The cooling water for the reflux condenser was then switched to hot water, and the temperature was raised to 220°C by removing water and toluene from the reflux condenser outlet, and the polycondensation reaction was carried out for 3 hours. After the polycondensation reaction, the polycondensation reaction product was removed from the bottom of the reaction vessel and allowed to cool and solidify. The solid product was pulverized in a Waring blender, washed with acetone, 1% oxalic acid water, and distilled water, and dried in a vacuum oven at 120°C for 16 hours to obtain 470 g of powder raw material polyethernitrile (hereinafter referred to as "aromatic polyethernitrile α") (yield 95%). The potassium content of the obtained aromatic polyethernitrile α was 10 ppm or less. The molecular weight of the obtained aromatic polyethernitrile α measured by the above analytical method is shown in Table 1.

[0048] Examples 1 to 3, Comparative Examples 1 to 5 The aromatic polyethernitrile α obtained in Synthesis Example 4 was powder-mixed with the aromatic ethernitrile composition α obtained in Synthesis Example 1, the comparative aromatic ethernitrile composition obtained in Synthesis Example 2, and the compound (6) obtained in Synthesis Example 3 as additives in the amounts shown in Table 2, and then melt-kneaded at 380°C under a nitrogen atmosphere under the following conditions, and a strand was obtained while measuring the melt viscosity of the aromatic polyethernitrile resin composition. (Melt-kneading conditions) Apparatus: Circulation kneader [Xplore MC15HT] (manufactured by Xplore Instrument) Temperature / time: 380°C / 5 min. Rotation speed: 100 rpm Screw shape: Conical twin screw Kneading environment: N ２The weight average molecular weight (Mw), number average molecular weight (Mn), glass transition temperature (Tg), and 1% weight loss temperature (Td1) of the resulting aromatic polyethernitrile resin composition and the aromatic polyethernitrile α obtained in Synthesis Example 4 were measured by the above-mentioned methods, and the results are shown in Table 2. The measurement results for the aromatic polyethernitrile α obtained in Synthesis Example 4 to which no additive was added are shown as Comparative Example 5.

[0049] The above Examples 1 to 3 are specific examples of the present invention in which aromatic polyethernitrile resin compositions were produced using aromatic polyethernitrile α as the aromatic polyethernitrile (B) and varying the blending amount of aromatic ethernitrile composition α as the aromatic ethernitrile composition (A). The above Examples 1 to 3 and Comparative Examples 1 to 5 confirmed that aromatic ethernitrile composition α, the comparative aromatic ethernitrile composition, and compound (6) have the effect of lowering melt viscosity when blended with aromatic polyethernitrile α. The aromatic polyethernitrile resin compositions containing the compositions and compounds used as additives in Comparative Examples 1 to 4 had 1% weight loss temperatures of 380°C or lower, and all of them generated gas during molding, such as injection or extrusion, which is likely to cause mold contamination and defective molded products. This result is thought to be due to the fact that the molecular weight of the compound represented by formula (2-1) in the comparative aromatic ethernitrile composition is as low as 322 and is highly volatile at low temperatures. The difference in thermal weight loss between the aromatic polyethernitrile resin compositions obtained using aromatic ethernitrile composition α and compound (6) as additives is thought to be due to the slight difference between the molecular weight of compound (1-1) (471) and the molecular weight of compound (6) (439), or the difference in affinity between compound (1-1) and compound (6) with aromatic polyethernitrile resulting from the presence or absence of a hydroxyl group.

[0050] Example 4 A polyimide film was placed on a 150 mm x 150 mm x 1 mm stainless steel plate, and a 20 mm wide spacer with a thickness of 0.12 mm, a vertical dimension of 80 mm, and a horizontal dimension of 60 mm was placed thereon. 1 g of the aromatic polyethernitrile resin composition obtained in Example 1 was filled into the spacer. A polyimide film was then placed on top of the polyimide film, and another 150 mm x 150 mm x 1 mm stainless steel plate was placed on top of the polyimide film (hereinafter, this set is referred to as the "molding mold"). The resulting assembly was then loaded onto the lower heating platen of a press molding machine (Toyo Seiki Mini Test Press MP-2FH, simulating the heating cylinder of an injection molding machine) that had been preheated to 380°C. After loading the "molding mold," the upper heating platen was immediately lowered to apply pressure. The pressure reached 10 MPa within 30 seconds, and the resin was melted at 380°C for 30 seconds. This 380 ° C. "molding mold" was removed from the hot platen and quickly loaded onto the lower hot platen of another press molding machine (Toyo Seiki Mini Test Press MP-2FH: assumed mold for injection molding machine) that had been preheated to 200 ° C. The upper hot platen was immediately lowered and a pressure of 10 MPa was applied, and the mold was maintained for 1 minute. After 1 minute, the "molding mold" was removed from the hot platen and rapidly cooled using an attached water-cooled cold press. The spacer with the aromatic polyether nitrile resin composition sheet sandwiched between polyimide films was removed from the "molding mold," and a sheet of aromatic polyether nitrile resin composition measuring 0.1 mm in thickness, 80 mm in length, and 60 mm in width was obtained. The degree of crystallinity calculated by measuring the heat of recrystallization and heat of fusion of the obtained aromatic polyether nitrile resin composition sheet using DSC was 8%. Furthermore, test pieces of the following sizes were prepared from the obtained sheets, and the tensile strength and tensile elongation were measured using a universal material testing machine AG-50kNXDplus (load cell: 5 kN: manufactured by Shimadzu Corporation) under the following conditions: Test piece shape: JIS K6251 dumbbell type No. 6 Test speed: 100 mm / min Test temperature / humidity: 23°C / 50% RH The results are shown in Table 3.

[0051] Examples 5 and 6, Comparative Example 6, Reference Example Using the aromatic polyethernitrile resin compositions and aromatic polyethernitriles and PEEK resins shown in Table 2, which had a 1% weight loss temperature of 380°C or higher, sheets were obtained in the same manner as in Example 4, and the crystallinity, tensile strength, and tensile elongation were measured. The results are shown in Table 3. From the above Examples 4 to 6 and Comparative Example 6, it is clear that the aromatic polyether nitrile resin composition of the present invention has an improved crystallization rate while maintaining mechanical strength equivalent to that of a base resin not containing the aromatic ether nitrile composition.

[0052] As described above, the aromatic polyethernitrile resin composition of the present invention can reduce the melt viscosity without impairing the heat resistance and mechanical strength of the aromatic polyethernitrile, and can improve the moldability without causing problems such as gas generation, thereby providing high-quality molded articles.

Claims

1. An aromatic polyethernitrile resin composition, in which the weight ratio of aromatic ethernitrile composition (A) to aromatic polyethernitrile (B) is in the range of (A) / (B) = 1 / 99 to 50 / 50, and the weight average molecular weight (Mw) measured by gel permeation chromatography analysis in terms of polystyrene is 45,000 or more. <Aromatic Ethernitrile Composition (A)> An aromatic ethernitrile composition containing a dihydroxy compound represented by general formula (1), which satisfies compositions (i) and (ii) in liquid chromatography (LC) analysis using ultraviolet light at a wavelength of 280 nm as a detector. Composition (i): The area percentage of the dihydroxy compound represented by general formula (1) is in the range of 10% to 95% of all components detected by the LC analysis. Composition (ii): The sum of the area percentages of the compound represented by general formula (2), the dihalobenzonitrile compound represented by general formula (3), and the dihydroxy compound represented by general formula (4) is 5% or less of all components detected by the LC analysis. (In general formulas (1), (2), and (4), R each independently represents a divalent group represented by general formula (1a) or (1b), and in general formulas (2) and (3), X each independently represents a halogen atom.) (In general formula (1a), R １ each independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, a phenyl group, a phenoxy group, or a phenylalkyl group having 7 to 10 carbon atoms; m represents 0 or an integer of 1 to 4; n represents 0 or 1; p and q represent 0, 1, or 2; and * represents each bonding position. (In general formula (1b), R １ and m are defined as in general formula (1a), Y represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group, Z represents an oxygen atom, a sulfur atom, or non-crosslinking, each Ar independently represents an aryl group having 6 to 8 carbon atoms, and * represents each bonding position.) <Aromatic Polyether Nitrile (B)> An aromatic polyether nitrile having a weight average molecular weight (Mw) of 50,000 or more in terms of polystyrene, as measured by gel permeation chromatography analysis, and having a repeating unit represented by general formula (5). (R in general formula (5) is defined the same as in general formulas (1), (2), and (4).) 2. The aromatic polyether nitrile resin composition according to claim 1, wherein R in the general formulas (1), (2) and (4) of the aromatic ether nitrile composition (A) and the general formula (5) of the aromatic polyether nitrile (B) are each independently a phenylene group, a naphthylene group or a biphenylene group.

3. The aromatic polyether nitrile resin composition according to claim 1, wherein the aromatic ether nitrile composition (A) further contains a polymer having a repeating unit represented by general formula (5). (R in general formula (5) is common to general formulas (1), (2), and (4), and each R is independently a divalent group represented by general formula (1a) or general formula (1b).) 4. The aromatic polyether nitrile resin composition according to claim 1, wherein the aromatic ether nitrile composition (A) has a weight average molecular weight (Mw) of 500 or more and 8,000 or less in terms of polystyrene as measured by gel permeation chromatography (GPC) analysis.

5. The aromatic polyether nitrile resin composition according to claim 1, wherein the weight ratio of the aromatic ether nitrile composition (A) to the aromatic polyether nitrile (B) is (A) / (B) in the range of 10 / 90 to 40 / 60.